Emulsifier-free finely dispersed water-in-oil type systems

ABSTRACT

Cosmetic or dermatological preparations which are finely disperse systems of the water-in-oil type, comprising
         1. an oil phase,   2. a water phase,   3. at least one modified phyllosilicate which exhibits both hydrophilic and lipophilic properties, i.e. which has amphiphilic character and positions itself at the water/oil interface and   4. at most 0.5% by weight of one or more emulsifiers and
 
optionally comprising further cosmetic or pharmaceutical auxiliaries, additives and/or active ingredients.

The present invention relates to emulsifier-free finely disperse systemsof the water-in-oil type, preferably as cosmetic or dermatologicalpreparations.

Emulsions are generally understood as meaning heterogeneous systemswhich consist of two liquids which are immiscible or only miscible withone another to a limited extent, which are normally referred to asphases. In an emulsion, one of the two liquids is dispersed in the otherliquid in the form of the very fine droplets.

If the two liquids are water and oil and if oil droplets are finelydistributed in water, then this is an oil-in-water emulsion (O/Wemulsion, e.g. milk). The basic character of an O/W emulsion isdetermined by the water. In the case of a water-in-oil emulsion (W/Oemulsion, e.g. butter), the principle is reversed, the basic characterhere being determined by the oil.

In order to achieve permanent dispersion of one liquid in another,emulsions in the traditional sense require the addition of asurface-active substance (emulsifier). Emulsifiers have an amphiphilicmolecular structure, consisting of a polar (hydrophilic) and a nonpolar(lipophilic) molecular moiety, which are spatially separate from oneanother. In simple emulsions, one phase comprises finely dispersedroplets of the second phase, surrounded by an emulsifier coating (waterdroplets in w/o emulsifiers or lipid vesicles in o/w emulsions).Emulsifiers lower the surface tension between the phases by positioningthemselves at the interface between two liquids. They form interfacialfilms at the oil/water phase boundary, as a result of which irreversiblecoalescence of the droplets is prevented. Emulsions are frequentlystabilized using emulsifier mixtures.

Traditional emulsifiers can, depending on their hydrophilic molecularmoiety, be divided into ionic (anionic, cationic and amphoteric) andnonionic:

-   -   The most well-known example of an anionic emulsifier is soap,        which is usually the term used for the water-soluble sodium or        potassium salts of saturated and unsaturated higher fatty acids.    -   Important examples of cationic emulsifiers are the quaternary        ammonium compounds.    -   The hydrophilic molecular moiety of nonionic emulsifiers        frequently consists of glycerol, polyglycerol, sorbitans,        carbohydrates and polyoxyethylene glycols and, in most cases, is        linked to the lipophilic molecular moiety via ester and ether        bonds. The lipophilic molecular moiety usually consists of fatty        alcohols, fatty acids or isofatty acids.        By varying the structure and the size of the polar and nonpolar        molecular moiety, the lipophilicity and hydrophilicity of        emulsifiers can be varied within wide limits.

A decisive factor for the stability of an emulsion is the correct choiceof emulsifiers. In this connection, the characteristics of all thesubstances present in the system are to be taken into consideration. Inthe case of, for example, skin care emulsions, polar oil components and,for example, UV filters lead to instability. As well as the emulsifiers,therefore, other stabilizers are also used which, for example, increasethe viscosity of the emulsion and/or act as protective colloid.

Emulsions represent an important product type in the field of cosmeticand/or dermatological preparations.

Cosmetic preparations are essentially used for skin care. The main aimof skin care in the cosmetics sense is to strengthen or rebuild theskin's natural function as the barrier against environmental influences(e.g. dirt, chemicals, microorganisms) and against the loss ofendogenous substances (e.g. water, natural fats, electrolytes). If thisfunction becomes impaired, increased resorption of toxic or allergenicsubstances or attack by microorganisms may result, leading to toxic orallergic skin reactions.

Another aim of skin care is to compensate for the loss by the skin oflipids and water caused by daily washing. This is particularly importantwhere the natural regeneration ability is inadequate. Furthermore,skincare products should protect against environmental influences, inparticular against sun and wind, and delay skin ageing.

Cosmetic preparations are also used as deodorants. Such formulations areused to control body odour which forms when fresh perspiration, which isin itself odourless, is decomposed by microorganisms.

Medicinal topical compositions usually comprise one or more medicamentsin an effective concentration. For the sake of simplicity. In order todistinguish clearly between cosmetic and medicinal use and correspondingproducts, reference is made to the legal provisions of the FederalRepublic of Germany (e.g. Cosmetics Directive, Food and Drugs Act).

The use of customary emulsifiers in cosmetic or dermatologicalpreparations is in itself acceptable. Nevertheless, emulsifiers, likeultimately any chemical substance, may in individual instances causeallergic reactions or reactions based on oversensitivity of the user.

For example, it is known that certain light dermatoses are triggered bycertain emulsifiers, but also by various fats and simultaneous exposureto sunlight. Such light dermatoses are also called “Mallorca acne”.There has thus been no lack of attempts to reduce the amount ofcustomary emulsifiers to a minimum, and in an ideal case evencompletely.

A reduction in the required amount of emulsifier can, for example, beachieved by taking advantage of the fact that very finely divided solidparticles have an additional stabilizing action. Here, this results inan accumulation of the solid substance at the oil/water phase boundaryin the form of a layer, as a result of which coalescence of the dispersephases is prevented. Of fundamental importance here are not the chemicalproperties, but the surface properties of the solid particles.

A relatively new technical development involves stabilizing cosmetic ordermatological preparations only using very finely divided solidparticles. Such “emulsifier-free” emulsions are also referred to asPickering emulsions after their inventor.

In this connection, basic experiments have shown that one characteristicof a Pickering emulsion is that the solid particles are arranged at theinterface between the two liquid phases, where they form, as it were, amechanical barrier against the combining of the liquid droplets.

One way of achieving solid stabilization in a cosmetic or dermatologicalpreparation, according to May-Alert (Pharmazie in unserer Zeit [Pharmacyin our Time], Vol. 15. 1986, No. 1, 1-7) for example, is to useemulsifier mixtures which comprise both anionic and cationicsurfactants. Since mixing anionic and cationic surfactants alwaysresults in the precipitation of insoluble, electroneutral compounds,deliberate precipitation of these neutral surfactants in the oil/waterinterface makes it possible to achieve additional solids stabilizationin the sense of a Pickering emulsion.

Moreover, European laid-open Specification 0 686 391 describes“emulsions” of the water-in-oil type which are free from surface-activesubstances and are stabilized only by solids. For the stabilization, useis made here of spherical polyalkylsilsesquioxane particles which have adiameter of from 100 nm to 20 μm, which are added to the oil phase andthicken said phase. This type of preparations can therefore also bereferred to as oil gels (also: oleogels), in which water can be stablydispersed.

In addition, the WO Specification WO-98/42301 describes emulsifier-freefinely disperse systems of the water-in-oil type which are stabilized bythe addition of micronized inorganic pigments which are chosen from thegroup of metal oxides, in particular titanium dioxide.

However, the prior art was unable to point the way to the presentinvention.

In addition to the described systems, the prior art recognizes furtheremulsifier-free, finely disperse cosmetic or dermatologicalpreparations, which are generally referred to as hydrodispersions.Hydrodispersions are dispersions of a liquid, semisolid or solidinternal (discontinuous) lipid phase in an external aqueous (continuous)phase.

In hydrodispersions of a liquid lipid phase in an external aqueousphase, the stability can, for example, be ensured by constructing a gelframework in the aqueous phase in which the lipid droplets are stablysuspended. German laid-pen Specification 44 25 268 describes stablefinely disperse, emulsifier-free cosmetic or dermatological preparationsof the oil-in-water type which, in addition to an oil and a water phase,comprise one or more thickeners from the group of acrylic acid polymers,polysaccharides and alkyl ethers thereof, where it must not be possibleto measure a reduction in the interfacial tension for these thickeners.

Based on similar hydrodispersions, German laid-open Specification 43 03983 discloses cosmetic or dermatological light protection formulationswhich are essentially free from emulsifiers, where inorganicmicropigments which serve as UV filter substances are incorporated intothe lipid phase of the hydrodispersion.

According to that stated above, Pickering emulsions are stabilized bythe use of suitable solids and/or pigments. However, when correspondingpreparations are applied on the skin, solids may leave behind a dry andsometimes harsh impression. Even preparations with a pigment content of1% by weight produce a harsh feel on the skin following theirapplication, which increases yet further with higher pigmentconcentrations. In individual cases, therefore, pigment-containingpreparations may not even be marketable since they are not accepted byand/or are viewed negatively by the consumer.

The object was therfore to overcome the disadvantages of the prior art.In particular, the aim was to provide preparations which do not leavebehind a dry or harsh impression on the skin.

A further object of the invention was to develop cosmetic anddermatological bases for cosmetic and dermatological preparations whichare characterized by good skin compatibility.

It was also an object of the present invention to provide products withthe widest possible variety of applications. For example, the intentionwas to provide bases for preparation forms such as cleansing emulsions,face care and body care preparations or deodorants but also distinctlymedicinal pharmaceutical administration forms, for example, preparationsagainst acne and other skin conditions.

A further object of the present invention was to enrich the prior artwith cosmetic or dermatological preparations in which any use ofemulsifiers of the traditional type can be dispensed with.

Surprisingly, all of these objects are achieved by cosmetic ordermatological preparations which are finely disperse systems of thewater-in-oil type, comprising

-   -   1. an oil phase,    -   2. a water phase,    -   3. at least one modified phyllosilicate which exhibits both        hydrophilic and lipophilic properties, i.e. which has        amphiphilic character and positions itself at the water/oil        interface and    -   4. at most 0.5% by weight of one or more emulsifiers and        optionally comprising further cosmetic or pharmaceutical        auxiliaries, additives and/or active ingredients.

According to the invention, it is particularly advantageous if thepreparations comprise significantly less than 0.5% by weight of one ormore emulsifiers. Very particular preference is given to preparationsaccording to the invention which are entirely free from emulsifiers inthe traditional sense.

The preparations according to the invention are mixtures of oils oroil-soluble substances and water or water-soluble components, which arestabilized by the addition of the modified phyllosilicate particles anddo not have to comprise an emulsifier in the traditional sense.

The preparations according to the invention are entirely satisfactorypreparations in every respect which, surprisingly, have excellentcosmetic properties, do not leave behind a dry or harsh impression onthe skin, and are characterized by excellent skin compatibility.

Modified Phyllosilicates

Silicates are salts and esters (silicic esters) of orthosilicic acid[Si(OH)₄] and condensation products thereof. Silicates are not only theclass of minerals which contain the most types, but are also extremelyimportant from a geological and industrial viewpoint. Over 80% of theearth's crust consists of silicates. Phyllosilicates are (ideally)silicate structures having two-dimensionally infinite layers of [SiO₄]⁴⁻tetrahedra, each tetrahedron being bonded to neighbouing tetrahedra by 3bridging oxygens.

Only approximate chemical formulae can be given for phyllosilicatessince they have a large ion-exchange capability, and silicon can bereplaced by aluminium, and this in turn can be replaced by magnesium,Fe²⁺, Fe³⁺, Zn and the like. The negative charge of the layers which mayresult is usually balanced by cations, in particular by Na⁺ and Ca²⁺ ininterlayer positions.

Phyllosilicates can swell by reversible intercalation of water (in a 2-to 7-fold amount) and other substances, such as, for example, alcohols,glycols and the like. Their use as thickeners in cosmetic compositionsis, accordingly, known per se. However, the prior art was unable topoint the way to the present invention.

Advantageous phyllosilicates for the purpose of the present inventionare, for example, those whose greatest expansion direction in theunmodified and unswollen state has, on average, a length of less than 10μm. For example, the average expansions of the modified phyllosilicateparticles used can be 1000 nm×100 nm×1 nm and below. The effective sizeof the modified phyllosilicate particles in a cosmetic or dermatologicalformulation naturally depends on the amount of intercalated substances.

Advantageous modified phyllosilicates for the purposes of the presentinvention are, for example, modified smectites.

Smectites are always very finely particulate (in most cases <2 mm)three-layer clay minerals (2:1 phyllosilicates) which occur mainly aslamella-shaped, moss-like or spherical aggregates, in which a centrallayer of octahedrally coordinated cations is sandwiched by two layers of[(Si₉Al)O₄] tetrahedra. Smectites are described in an idealized mannerby the following structural formula, in which circles filled in whiterepresent silicon and/or aluminium atoms, circles filled in pale greyare oxygen atoms, circles filled in dark grey are hydrogen atoms, andcircles filled in black are aluminium, magnesium, iron atoms and/orother exchange cations:

Advantageous modified smectites are, for example, modifiedmontmorillonites. Montmorillonites are described by the approximatedchemical formula Al₂[(OH)₂/Si₄O₁₀].nH₂O or Al₂O₃.4Si₂.H₂O.nH₂O, and areclay minerals belonging to the dioctahedral smectites.

Also particularly advantageous for the purposes of the present inventionare, for example, modified hectorites. Hectorites are types of smectitesand have the approximate chemical formula M⁺_(0.3)(Mg_(2.7)Li_(0.3))[Si₄O₁₀(OH)₂], in which M⁺ is in most cases Na⁺.

Also advantageous for the purposes of the present invention are modifiedbentonites. Bentonites are clays and rocks which contain smectites,especially montmorillonite, as main minerals. The “crude” bentonites areeither calcium bentonites (referred to in Great Britain as fuller'searths) or sodium bentonites (also: Wyoming bentonites).

Modified phyllosilicates for the purposes of the present invention arephyllosilicates, in particular the phyllosilicate types alreadymentioned, whose organophilicity (also: lipophilicity) has beenincreased, for example by reaction with quaternary ammonium compounds.Such phyllosilicates are also referred to as organophillicphyllosilicates.

Particularly advantageous for the purposes of the present invention arebentones, i.e. organic derivatives of montmorillonites (or bentonites)and/or hectorites, which are prepared by ion-exchange reactions withalkylammonium bases.

Advantageous modified phyllosilicates for the purposes of the presentinvention are obtainable, for example, by reacting phyllosilicates withquaternium-18. Quaternium-18 is a mixture of quarternary ammoniumchloride salts which are described by the following structural formula:

in which

-   the radicals R¹ are independently of one another chosen from the    group consisting of methyl and hydrogenated tallow radicals having a    chain length of from 12 to 20 carbon atoms.

According to the invention, particular preference is given tostearalkonium hectorite, a reaction product of hectorite andstearalkonium chloride (benzyldimethylstearyl-ammonium chloride), andquaternium-18 hectorite, a reaction product of hectorite andquaternium-18, which are available, for example, under the trade namesBentone 27 and Bentone 38 from Nordmann & Rassmann.

The total amount of one or more modified phyllosilicates in the finishedcosmetic or dermatological preparations is advantageously chosen fromthe range 0.05 to 20.0% by weight, preferably 0.1 to 5.0% by weight,based on the total weight of the preparations.

Although it is particularly preferred to stabilize the preparationsaccording to the invention only by the addition of one or more modifiedphyllosilicates, it may also be advantageous to combine the modifiedphyllosilicate particles with further amphiphilic pigments which mayalso contribute to the stabilization of the Pickering emulsions.

Such pigments are for example, micronized, inorganic pigments chosenfrom the group of amphiphilic metal oxides, in particular from the groupconsisting of titanium dioxide, zinc oxide, silicon dioxide andsilicates (e.g. talc), it being possible for the metal oxides to bepresent individually or as a mixture. In this connection, it isessentially unimportant in which of the potentially naturally occurringmodifications the amphiphilic metal oxides used are present.

It is advantageous to choose the average particle diameter of thepigments used in combination with modified phyllosilicates to be between1 nm and 200 nm, particularly advantageously between 5 nm and 100 nm.

For the purposes of the present invention, it is advantageous to combinethe modified phyllosilicates according to the invention with untreated,virtually pure pigment particles, in particular with those which canalso be used as dye in the foods industry and/or as absorbers of UVradiation in sunscreens. Advantageous examples are the zinc oxidepigments available from Merck, and those available under the trade namesZinkoxid neutral from Haarmann & Reimer or NanoX from Harcros ChemicalGroup.

According to the invention the combination of modified phyllosilicateswith inorganic pigments which have been surface-treated (“coated”) torepel water is also advantageous, the intention being for theamphiphilic character of these pigments to be formed or retained at thesame time. This surface treatment may involve providing the pigmentswith a thin hydrophobic layer by methods known per se.

Such a process, which is described below using tit anium dioxide as anexample, consists, for example, in producing the hydrophobic surfacelayer by a reaction in accordance withnTiO₂+m(RO)₃Si—R′→+nTiO₂ (surf.)n and m are stoichiometric parameters to be used as desired, and R andR′ are the desired organic radicals. Particularly advantageouscombination partners are TiO₂ pigments, for example, those coated withaluminium stearate and obtainable under the trade name MT 100 T fromTAYCA.

A further advantageous coating of the combination partners consists ofdimethylpolysiloxane (also: dimethicone), a mixture of completelymethylated, linear siloxane polymers which have been terminally blockedwith trimethylsiloxy units. The combination of modified phyllosilicateswith zinc oxide pigments which have been coated in this manner isparticularly advantageous for the purposes of the present invention.

It also advantageous if the inorganic pigments used in addition tomodified phyllosilicates have been coated with a mixture ofdimethylpolysiloxane, in particular dimethylpolysiloxane having anaverage chain length of from 200 to 350 dimethylsiloxane units, andsilica gel, which is also referred to as simethicone. It is particularlyadvantageous if the inorganic pigments have been additionally coatedwith aluminium hydroxide or hydrated aluminium oxide (also: alumina, CASNo.: 1333-84-2). Particularly advantageous combination partners aretitanium dioxides which have been coated with simethicone and alumina,it also be possible for the coating to comprise water. One examplethereof is the titanium dioxide available under the trade name EusolexT2000 from Merck.

The combination of modified phyllosilicates with a mixture of differentinorganic, amphiphilic pigment types, either within a crystal, forexample as iron mixed oxide or talc (magnesium silicate) or else bymixing two or more types of metal oxide within a preparation is alsoadvantageous for the purposes of the present invention. Magnesiumsilicates are particularly advantageous combination partners, forexample those available under the trade name Talkum Micron fromGrolmann.

The modified phyllosilicates according to the invention can alsoadvantageously be combined with other pigments, for example, withtitanium dioxide pigments which have been coated with octylsilanol,and/or with silicon dioxide particles which have been surface-treated torepel water. Silicon dioxide particles suitable for the combination are,for example, spherical polyalkylsilsesquioxane particles, as mentionedin European Laid-Open Specification 0 686 391. Suchpolyalkylsilsesquioxane particles are available, for example, under thetrade names Aerosil R972 and Aerosil 200V from Degussa.

It is further advantageous to combine the modified phyllosilicates withmicrofine polymer particles which are in the preparation in the form ofsolids. Favourable examples of combination partners for the purposes ofthe present invention are polycarbonates, polyethers, polyethylene,polypropylene, polyvinyl chloride, polystyrene, polyamides,polyacrylates and the like.

According to the invention, suitable examples of combination partnersare microfine polyamide particles, in particular those available underthe trade name SP-500 from TORAY. Also advantageous are polyamide 6(also: nylon 6) and polyamide 12- (also: nylon 12) particles. Polyamide6 is the polyamide [poly(ε-caprolactam)], built up from ε-aminocaproicacid (6-aminohexanoic acid) or ε-caprolactam, and polyamide 12 is apoly(ε-laurolactam) of ε-laurolactam. Advantageous examples for thepurposes of the present invention are Orgasol® 1002 (polyamide 6) andOrgasol® 2002 (polyamide 12) from ELF ATOCHEM.

Further advantageous microfine polymer particles which are suitable forcombination with the modified phyllosilicates according to the inventionare microfine polymethacrylates. Such particles are available, forexample, under the trade name POLYTRAP° from DOW CHEMICAL.

It is particularly advantageous, although not obligatory, if themicrofine polymer particles used as combination partners have beensurface-coated. This surface treatment can involve providing the polymerparticles with a thin hydrophilic layer by processes known per se.Advantageous coatings consist, for example, of titanium dioxide (TiO₂),zirconium dioxide (ZrO₂) or else further polymers, such as, for example,polymethyl methacrylate. Particularly advantageous microfine polymerparticles for the purposes of the present invention are, for example,those available by the process described in U.S. Pat. No. 4,898,913 forthe hydrophilic coating of hydrophobic polymer particles.

The average particle diameter of the microfine polymer particles used ascombination partners is preferably chosen to be less than 100 μm,particularly advantageously to be less than 50 μm. In this connection,it is essentially unimportant in which form (platelets, rods, spherulesetc.) the polymer particles used are present.

The modified phyllosilicates according to the invention are alsopreferably combined with amphiphilic modified polysaccharides which donot exhibit thickening properties.

Such amphiphilic polysaccharides are obtainable, for example, byreacting starch with mono-, bi- or polyfunctional reagents or oxidizingagents in reactions which proceed in a predominantly polymer-analogousmanner.

These reactions are based essentially on modifications of the hydroxylgroups of the polyglucans by etherification, esterification or selectiveoxidation. This produces, for example, starch ethers and starch estersof general structural formula

in which R can, for example, be a hydrogen and/or an alkyl and/oraralkyl radical (in the case of starch ethers) or a hydrogen and/or anorganic and/or an inorganic acid radical (in the case of starch esters).Starch ethers and starch esters are advantageous combination partnersfor the purposes of the present invention.

It is particularly advantageous to combine the modified phyllosilicatesaccording to the invention with starch ethers, e.g. with thoseobtainable by etherifying starch with tetramethylolacetylenediurea andwhich are referred to as Amylum non mucilaginosum (nonswelling starch).

Also particularly advantageous is the combination of modifiedphyllosilicates according to the invention with starch esters and/orsalts thereof, for example with sodium and/or aluminium salts ofhalf-esters of starch which have low degrees of substitution, inparticular with sodium starch n-octenyl succinate of the structuralformula (I) in which R is characterized by the following structure

and which is available, for example, under the trade name Amiogum® 23from CERESTAR, and with aluminium starch octenyl succinate, inparticular with those available under the trade names Dry Flo® Elite LLand Dry Flo® PC from CERESTAR.

It is advantageous to choose the average particle diameter of themodified polysaccharides used for the combination with the modifiedphyllosilicates according to the invention to be less than 20 μm,particularly advantageously less than 15 μm.

The list of given modified polysaccharides which can be combined withthe modified phyllosilicates is not of course intended to be limiting.Modified polysaccharides which are advantageous combination partners forthe purposes of the present invention are obtainable in numerous ways,either chemical or physical in nature, which are known per se. For thepreparation of such polysaccharides, novel ways are in principle alsoconceivable. In this connection, it is important that the modifiedpolysaccharides display amphiphilic properties and that they do not havea thickening action.

In all of the abovementioned cases it is advantageous to choose theoverall concentration of all pigments to be greater than 0.05% byweight, particularly advantageously between 0.05% and 30% by weight,based on the total weight of the preparations, where the concentrationof modified phyllosilicates—likewise based on the total weight of thepreparations—for the purposes of the present invention is to be chosenpreferably from the range from 0.05% to 30% by weight, advantageously0.1% to 10% by weight.

The Pickering emulsions according to the invention can be used as basesfor cosmetic or dermatological formulations. The latter can have thecustomary composition and be used, for example, for the treatment andcare of the skin, as lip care product, as deodorant product and asmake-up or make-up remover product in decorative cosmetics or as a lightprotection preparation. For use, the cosmetic and dermatologicalpreparations according to the invention are applied to the skin in asufficient amount in the manner customary for cosmetics.

Accordingly, for the purposes of the present invention, cosmetics ortopical dermatological compositions can, depending on their composition,be used, for example, as skin protection cream, cleansing milk,sunscreen lotion, nourishing cream, day or night cream etc. In someinstances, it is possible and advantageous to use the compositionsaccording to the invention as bases for pharmaceutical formulations.

The cosmetic and dermatological preparations according to the inventioncan comprise cosmetic auxiliaries, as are customarily used in suchpreparations, e.g. preservatives, bactericides, perfumes, antifoams,dyes, pigments which have a colouring action, thickeners, emollients,moisturizers and/or humectants, fats, oils, waxes or other customaryconstituents of a cosmetic or dermatological formulation, such asalcohols, polyols, polymers, foam stabilizers, electrolytres, organicsolvents or silicone derivatives.

A surprising property of the preparations according to the invention isthat they are very good vehicles for cosmetic or dermatological activeingredients into the skin, advantageous active ingredients beingantioxidants which are able to protect the skin against oxidativestress.

According to the invention, the preparations advantageously comprise oneor more antioxidants. Antioxidants which are favourable, butnevertheless optional, are all antioxidants which are suitable orcustomary for cosmetic and/or dermatological applications. It isadvantageous to use antioxidants as the sole active ingredient classwhen, for example, any cosmetic or dermatological application is at thefore, such as, for example, the control of oxidative stress of the skin.It is, however, also favourable to provide the stick preparationsaccording to the invention with a content of one or more antioxidants ifthe intention is for the preparations to have another purpose, e.g. asdeodorants or sunscreens.

The antioxidants are particularly advantageously chosen from the groupconsisting of amino acids (e.g. glycine, histidine, lyrosine,tryptophan) and derivatives thereof, imidazoles, (e.g. urocanic acid)and derivatives thereof, peptides, such as D,L-camosine, D-carnosine,L-carnosine and derivatives thereof (e.g. anserine), carotenoids,carotenes (e.g. α-carotene, β-carotene, lycopene) and derivativesthereof, chlorogenic acid and derivatives thereof, lipoic acid andderivatives thereof (e.g. dihydrolipoic acid), aurothioglucose,propylthiouracil and other thiols (e.g. thioredoxin, glutathione,cysteine, cystine, cystamine and the glycosyl, N-acetyl, methyl, ethyl,propyl, amyl, butyl and lauryl, palmitoyl, oleyl, γ-linoleyl,cholesteryl and glyceryl esters thereof) and salts thereof, dilaurylthiodipropionate, distearyl thiodipropionate, thiodipropionic acid andderivatives thereof (esters, ethers, peptides, lipids, nucleotides,nucleosides and salts) and sulphoximine compounds (e.g. buthioninesulphoximines, homocysteine sulphoximine, buthionine sulphones, penta-,hexa-, heptathionine sulphoximines) in very low tolerated doses (e.g.pmol to μmol/kg), and also (metal) chelating agents (e.g. α-hydroxyfattyacids, palmitic acid, phytic acid, lactoferrin), α-hydroxy acids (e.g.citric acid, lactic acid, malic acid), humic acid, bile acid, bileextracts, bilirubin, biliverdin, EDTA, EGTA and derivatives thereof,unsaturated fatty acids and derivatives thereof (e.g. γ-linolenic acid,linoleic acid, oleic acid), folic acid and derivatives thereof,ubiquinone and ubiquinol and derivatives thereof, vitamin C andderivatives (e.g. ascorbyl palmitate, Mg ascorbyl phosphate, ascorbylacetate), tocopherols and derivatives (e.g. vitamin E acetate), vitaminA and derivatives (vitamin A palmitate) and coniferyl benzoate ofbenzoin resin, ferulic acid, furfurylideneglucitol, carnosine, butylatedhydroxytoluene, butylated hydroxyanisole, nordihydroguaiac acid,nordihydroguaiaretic acid, trihydroxybutyrophenone, uric acid andderivatives thereof, mannose and derivatives thereof, zinc andderivatives thereof (e.g. ZnO, ZnSO₄), selenium and derivatives thereof(e.g. selenomethionine), stilbenes and derivatives thereof (e.g.stilbene oxide, trans-stilbene oxide), and the derivatives (salts,esters, ethers, sugars, nucleotides, nucleosides, peptides and lipids)of said active substances which are suitable according to the invention.

The amount of abovementioned antioxidants (one or more compounds) in thepreparations according to the invention is preferably 0.001 to 30% byweight, particularly preferably 0.05 to 20% by weight, in particular 0.1to 10% by weight, based on the total weight of the preparation.

If vitamin E and/or derivatives thereof are the antioxidant(s), it isadvantageous to choose their respective concentrations from the range0.001 to 10% by weight, based on the total weight of the formulation.

If vitamin A or vitamin A derivatives, or carotenes or derivativesthereof are the antioxidant(s), it is advantageous to choose theirrespective concentrations from the range 0.001 to 10% by weight, basedon the total weight of the formulation.

According to the invention, the active ingredients (one or morecompounds) can also very advantageously be chosen from the group oflipophilic active ingredients, in particular from the following group:

Acetylsalicylic acid, atropine, azulene, hydrocortisone and derivativesthereof, e.g. hydrocortisone-17 valerate, vitamins, e.g. ascorbic acidand derivatives thereof, vitamins of the B and D series, very favourablyvitamin B₁, vitamin B₁₂ and vitamin D₁, but also bisabolol, unsaturatedfatty acids, namely the essential fatty acids (often also called vitaminF), in particular gamma-linolenic acid, oleic acid, eicosapentaenoicacid, docosa-hexaenoic acid and derivatives thereof, chloramphenicol,caffeine, prostaglandins, thymol, camphor, extracts or other products ofa vegetable or animal origin, e.g. evening primrose oil, starflower oilor currant seed oil, fish oils, cod-liver oil or also ceramides andceramide-like compounds and so on.

It is also advantageous to choose the active ingredients from the groupof refatting substances, for example purcellin oil, Eucerit® andNeocerit®.

The list of specified active ingredients or active ingredientcombinations which can be used in the Pickering emulsions according tothe invention should not of course be limiting.

Cosmetic and dermatological preparations which are in the form of asunscreen are also favourable. In addition to the active ingredientcombinations according to the invention, these preferably additionallycomprise at least one UV-A filter substance and/or at least one UV-Bfilter substance. Such formulations can, although it is not necessary,optionally also comprise one or more inorganic pigments as UV filtersubstances.

Inorganic pigments based on metal oxides and/or other metal compoundswhich are insoluble or sparingly soluble in water are preferablypresent, in particular the oxides of titanium (TiO₂), zinc (ZnO), iron(e.g. Fe₂O₃), zirconium (ZrO₂), silicon (SiO₂), manganese (e.g. MnO),aluminium (Al₂O₃), cerium (e.g. Ce₂O₃), mixed oxides of thecorresponding metals, and mixtures of such oxides.

An additional content of stabilizing titanium dioxide and/or zinc oxideparticles can of course also be advantageous, but is not necessary forthe purposes of the present invention.

For the purposes of the present invention, it is also advantageous toprepare cosmetic and dermatological preparations whose main purpose isnot protection against sunlight, but which nevertheless contain UVprotection substances. Thus, for example, UV-A and UV-B filtersubstances are usually incorporated into day creams.

Also, UV protectants, like antioxidants, and if desired, preservatives,provide effective protection of the preparations themselves againstspoilage.

Preparations according to the invention advantageously comprisesubstances which absorb UV radiation in the UV-A and UV-B region, thetotal amount of filter substances being, for example, from 0.1% byweight to 30% by weight, preferably from 0.5 to 20% by weight, inparticular from 1.0 to 15% by weight, based on the total weight of thepreparations, in order to provide cosmetic preparations which protectthe hair and the skin from the entire range of ultraviolet radiation.They can also be used as sunscreens for the hair or the skin.

Advantageous UV-A filter substances for the purposes of the presentinvention are dibenzoyl methane derivatives, in particular4-(tert-butyl)-4′-methoxydibenzoylmethane (CAS No. 70356-09-1), which issold by Givaudan under the name Parsol® 1789 and by Merck under thetrade name Eusolex® 9020.

Further advantageous UV-A filter substances arephenylene-1,4-bis-(2-benzimidazyl)-3,3′-5,5′-tetrasulphonic acid:

and its salts, particularly the corresponding sodium, potassium ortriethanolammonium salts, in particularphenylene-1,4-bis-(2-benzimidazyl)-3,3′-5,5′-tetrasulphonic bis-sodiumsalt:

and 1,4-di(2-oxo-10-sulpho-3-bornylidenemethyl)benzene and salts thereof(in particular the corresponding 10-sulphato compounds, in particularthe corresponding sodium, potassium or triethanolammonium salt), whichis also referred to asbenzene-1,4-di(2-oxo-3-bornylidenemethyl-10-sulphonic acid) and ischaracterized by the following structure:

Advantageous UV filter substances for the purposes of the presentinvention are also broadband filters, i.e. filter substances whichabsorb both UV-A and also UV-B radiation.

Advantageous broad-band filters and/or UV-B filter substances are, forexample, bisresorcinyltriazine derivates having the following structure:

where R¹, R² and R³ independently of one another are chosen from thegroup of branched and unbranched alkyl groups having 1 to 10 carbonatoms, or are a single hydrogen atom. Particular preference is given to2,4-bis-[(4-(2-ethylhexyloxy)-2-hydroxy]phenyl)-6-(4-methoxyphenyl)-1,3,5-triazine(INCI: Aniso Triazine), which is available under the trade nameTinosorb® S from CIBA-Chemikelien GmbH and to tris(2-ethylhexyl)4,4′,4″-(1,3,5-triazine-2,4,6-triyltriimino)trisbenzoate, synonym:2,4,6-tris[anilino-(p-carbo-2′-ethyl-1′-hexyloxy)]-1,3,5-triazine (INCl:Octyl Triazone), which is marketed by BASF Aktiengesellschaft under thetrade name UVINUL® T 150.

Other UV filter substances, which have the structural formula

are also advantageous UV filter substances for the purposes of thepresent invention, for example the s-triazine derivatives described inEuropean Laid-Open Specification EP 570 838 A1, whose chemical structureis expressed by the generic formula

where

-   R is a branched or unbranched C₁-C₁₈-alkyl radical, a    C₅-C₁₂-cycloalkyl radical, optionally substituted with one or more    C₁-C₄-alkyl groups,-   X is an oxygen atom or an NH group,-   R₁ is a branched or unbranched C₁-C₁₈-alkyl radical, a    C₅-C₁₂-cycloalkyl radical, optionally substituted by one or more    C₁-C₄-alkyl groups, or a hydrogen atom, an alkali metal atom, an    ammonium group or a group of the formula    -   in which    -   A is a branched or unbranched C₁-C₁₈-alkyl radical, a        C₅-C₁₂-cycloalkyl or aryl radical, optionally substituted by one        or more C₁-C₄-alkyl groups,    -   R₃ is a hydrogen atom or a methyl group,    -   n is a number from 1 to 10,-   R₂ is a branched or unbranched C₁-C₁₈-alkyl radical, a    C₅-C₁₂-cycloalkyl radical, optionally substituted by one or more    C₁-C₄-alkyl groups, when X is the NH group, and    -   a branched or unbranched C₁-C₁₈-alkyl radical, a        C₅-C₁₂-cycloalkyl radical, optionally substituted by one or more        C₁-C₄-alkyl groups, or a hydrogen atom, an alkali metal atom, an        ammonium group or a group of the formula    -   in which    -   A is a branched or unbranched C₁-C₁₈-alkyl radical, a        C₅-C₁₂-cycloalkyl or aryl radical, optionally substituted by one        or more C₁-C₄-alkyl groups,    -   R₃ is a hydrogen atom or a methyl group,    -   n is a number from 1 to 10,    -   when X is an oxygen atom.

A particularly preferred UV filter substance for the purposes of thepresent invention is also an unsymmetrically substituted s-triazine, thechemical structure of which is expressed by the formula

and which is also referred to below as dioctylbutylamidotriazone (INCI:dioctylbutamidotriazone) and is available under the trade name UVASORBHEB from Sigma 3V.

European Laid-Open Specification 775 698 also describes preferredbisresorcinyltriazine derivatives, the chemical structure of which isexpressed by the generic formula

where R₁, R₂ and A₁ represent very different organic radicals.

Also advantageous for the purposes of the present invention are2,4-bis{[4-(3-sulphonato)-2-hydroxypropyloxy)-2-hydroxy]phenyl}-6-(4-methoxyphenyl)-1,3,5-triazinesodium salt,2,4-bis{[4-(3-(2-propyloxy)-2-hydroxypropyloxy)-2-hydroxy]phenyl})-6-(4-methoxyphenyl)-1,3,5-triazine,2,4-bis{[4-(2-ethylhexyloxy)-2-hydroxy]phenyl}-6-[4-(2-methoxyethylcarboxyl)phenylamino]-1,3,5-triazine,2,4-bis{[4-(3-(2-propyloxy)-2-hydroxypropyloxy)-2-hydroxy]phenyl}-6-[4-(2-ethylcarboxyl)phenylamino]-1,3,5-triazine,2,4-bis-{[4-(2-ethylhexyloxy)-2-hydroxy]phenyl}-6-(1-methylpyrrol-2-yl)-1,3,5-triazine,2,4-bis{[4-tris(trimethylsiloxysilylpropyloxy)-2-hydroxy]phenyl}-6-(4-methoxyphenyl)-1,3,5-triazine,2,4-bis{[4-(2″-methylpropenyloxy)-2-hydroxy]phenyl}-6-(4-methoxyphenyl)-1,3,5-triazineand2,4-bis{[4-(1′,1′,1′,3′,5′,5′,5′-heptamethylsiloxy-2″-methylpropyloxy)-2-hydroxy]-phenyl}-6-(4-methoxyphenyl)-1,3,5-triazine.

An advantageous broad-band filter for the purposes of the presentinvention is2,2′-methylenebis(6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol),which is characterized by the chemical structural formula

and is available under the trade name Tinosorb® M from CIBA-ChemikalienGmbH.

Another advantageous broad-band filter for the purposes of the presentinvention is2-(2H-benzotriazol-2-yl)-4-methyl-6-[2-methyl-3-[1,3,3,3-tetramethyl-1-[(trimethylsilyl-oxy]disiloxanyl]propyl]phenol(CAS No.: 155633-54-8) having the INCI name Drometrizole Trisiloxane,which is characterized by the chemical structural formula

The UV-B filters can be oil-soluble or water-soluble. Examples ofadvantageous oil-soluble UV-B filter substances are:

-   -   3-benzylidenecamphor derivatives, preferably        3-(4-methylbenzylidene)camphor, 3-benzylidenecamphor;    -   4-aminobenzoic acid derivatives, preferably 2-ethylhexyl        4-(dimethylamino)benzoate, amyl 4-(dimethylamino)benzoate;    -   2,4,6-trianilino(p-carbo-2′-ethyl-1′-hexyloxy)-1,3,5-triazine;    -   esters of benzalmalonic acid, preferably di(2-ethylhexyl)        4-methoxybenzalmalonate,    -   esters of cinnamic acid, preferably 2-ethylhexyl        4-methoxycinnamate, isopentyl 4-methoxycinnamate;    -   derivates of benzophenone, preferably        2-hydroxy-4-methoxybenzophenone,        2-hydroxy-4-methoxy-4′-methylbenzophenone,        2,2′-dihydroxy-4-methoxybenzophenone    -   and UV filters bonded to polymers.

Examples of advantageous water-soluble UV-B filter substances are: asalts of 2-phenylbenzimidazole-5-sulphonic acid, such as its sodium,potassium or its triethanolammonium salt, and also the sulphonic aciditself;

-   -   a sulphonic acid derivatives of 3-benzylidenecamphor, such as,        for example, 4-(2-oxo-3-bornylidenemethyl)benzenesulphonic acid,        2-methyl-5-(2-oxo-3-bornylidenemethyl)sulphonic acid and salts        thereof.

A further light protection filter substance which can be usedadvantageously according to the invention is ethylhexyl2-cyano-3,3-diphenylacrylate (octocrylene), which is available from BASFunder the name Uvinul® N 539 and is characterized by the followingstructure:

It can also be of considerable advantage to use polymer-bonded orpolymeric UV filter substances in the preparations according to thepresent invention, in particular those described in WO-A-92/20690.

In some instances, it can also be advantageous to incorporate furtherUV-A and/or UV-B filters in accordance with the invention into cosmeticor dermatological preparations, for example certain salicylic acidderivatives, such as 4-isopropylbenzyl salicylate, 2-ethylhexylsalicylate (=octyl salicylate), homomenthyl salicylate.

The list of given UV filters which can be used for the purposes of thepresent invention is not of course intended to be limiting.

Preparations according to the invention can also advantageously be usedas bases for cosmetic deodorants a nd antiperspirants so that aparticular embodiment of the present invention relates to Pickeringemulsions as bases for cosmetic deodorants.

Cosmetic deodorants are used to control body odour which forms whenfresh sweat, which is in itself odourless, is decomposed bymicroorganisms. Customary cosmetic deodorants are based on various modesof action.

In antiperspirants, astringents, mainly aluminium salts, such asaluminium hydroxychloride (aluminium chlorohydrate), can reduce sweatformation.

The use of antimicrobial substances in cosmetic deodorants can reducethe bacterial flora of the skin. In an ideal situation, only themicroorganisms which cause the odour would be effectively reduced. Theflow of sweat itself is not influenced as a result, and in idealcircumstances, only microbial decomposition of sweat is stoppedtemporarily.

The combination of astringents and antimicrobial active substances inone and the same composition is also common.

All active ingredients common for deodorants or antiperspirants canadvantageously be used, for example odour concealers, such as customaryperfume constituents, odour-absorbers, for example the phyllosilicatesdescribed in German Patent 40 09 347, of these in particularmontmorillonite, kaolinite, illite, beidellite, nontronite, saponite,hectorite, bentonite, smectite, and also, for example, zinc salts ofricinoleic acid. Antibacterial agents are also suitable to beincorporated into the W/O emulsion sticks according to the invention.Advantageous substances are, for example, 2,4,4′-trichloro-2′-hydroxydiphenyl ether (Irgasan), 1,6-di(4-chlorophenylbiguanido)hexane(chlorhexidine), 3,4,4′-trichlorocarbanilide, quaternary ammoniumcompounds, oil of cloves, mint oil, thyme oil, triethyl citrate,farnesol (3,7,11-trimethyl-2,6,10-dodecatrien-1-ol) and also the activeingredients or active ingredient combinations described in PatentLaid-Open Specifications DE 37 40 186, DE 39 38 140, DE 42 04 321, DE 4229 707, DE 43 09 372, DE 44 11 664, DE 195 41 967, DE 195 43 695, DE 19543 696, DE 195 47 160, DE 196 02 108, DE 196 02 110, DE 196 02 111, DE196 31 003, DE 196 31 004 and DE 196-34 019, and the patentspecifications DE-42 29-737, DE-42 37 081, DE-43 24 219, DE-44 29 467,DE-44 23 410 and DE-195 16 705. Sodium hydrogencarbonate can also beused advantageously.

The list of specified active ingredients and active ingredientcombinations which can be used in the novel Pickering emulsions is ofcourse not intended to be limiting.

The cosmetic deodorants according to the invention can be in the form ofaqueous, cosmetic preparations which can be applied from standardcontainers.

The amount of antiperspirant active ingredients or deodorants (one ormore compounds) in the preparations is preferably from 0.01 to 30% byweight, particularly preferably from 0.1 to 20% by weight, in particular1 to 10% by weight, based on the total weight of the preparation.

The sticks according to the invention are additionally excellentvehicles for dermatological active ingredients. In particular, they aresuitable as carriers for substances effective against acne. Acne is askin disorder with many forms and causes, characterized by noninflamedand inflamed bumps, originating from blocked hair follicles (comedones)which can lead to the formation of pustules, abscesses and scars. Themost frequent is Acne vulgaris, which occurs predominantly in puberty.Causative conditions for Acne vulgaris are the keratinization andblocking of the hair follicle opening, the production of sebum, which isdependent on the level of male sex hormones in the blood, and theproduction of free fatty acids and tissue-damaging enzymes by bacteria(Propionibacterium acnes).

It is therefore advantageous to add to the preparations according to theinvention, substances which are effective against acne, which are, forexample effective against Propionibacterium acnes (for example thosedescribed in DE-A 42 29 707, DE-A 43 05 069, DE-A 43 07 976, DE-A 43 37711, DE-A 43 29 379) but also other substances which are effectiveagainst acne, for example all-trans-retinoic acid, 13-cis-retinoic acidand related substances) or antinflammatory active ingredients, forexample batyl alcohol α-octadecyl glyceryl ether), selachyl alcohol(α-9-octadecenyl glyceryl ether), chirnyl alcohol (α-hexadecyl glycerylether) and/or bisabolol and antibiotics and/or keratolytcs.

Keratolytics are substances which soften keratinized skin (such as, forexample, warts, corns, calluses and the like) so that it can be removedmore easily or so that it falls off or peels off.

All of the common substances effective against acne can be usedadvantageously, in particular benzoyl peroxide, bituminosulphonates(ammonium, sodium and calcium salts of shale oil sulphonic acids),salicylic acid (2-hydroxybenzoic acid), miconazole(1-[2-(2,4-dichlorobenzyloxy)-2-(2,4-dichlorophenyl)ethyl]imidazole) andderivatives, adapalene (6-[3-(1-adamantyl)-4-methoxyphenyl]-2-naphthoicacid), azelaic acid (nonanedioic acid), mesulfene(2,7-dimethylthianthrene, C₁₄H₁₂S₂) and aluminium oxide, zinc oxideand/or finely dispersed sulphur.

The amount of antiaccne agents (one or more compounds) in thepreparations is preferably from 0.01 to 30% by weight, particularlypreferably 0.1 to 20% by weight, in particular 1 to 10% by weight, basedon the total weight of the preparation.

The examples below serve to illustrate the present invention withoutlimiting it. The numerical values in the examples are percentages byweight, based on the total weight of the respective preparations.

EXAMPLES

1 2 3 4 5 6 7 Bentone 38 ® 0.5 1 0.2 0. 0.5 Bentone 27 ® 0.3 0.7 0.3Polyglyceryl-2 dipoly- 0.2 hydroxystearate Cetyldimethicone copolyol 0.3PEG-30 dipolyhydroxy- 0.2 stearate Caprylic/capric triglyceride 10 5 5Octyldodecanol 10 10 5 Dicaprylyl ether 5 5 5 5 Cetearyl isononanoate 2Dimethicone 2 1 2 5 5 Mineral oil 5 10 5 5 2 Isohexadecane 2 5Hydrogenated 2 5 5 polyisobutene Butylene glycol dicapry- 2 5 5 5 8late/caprate C₁₂₋₁₅ Alkylbenzoate 7 3 5 Vitamin E acetate 0.5 0.5 0.50.5 0.5 Dioctylbutamidotriazone 3 1 Octocrylene 5 8 6 5 Octyltriazone 14 4 Methylbenzylidenecamphor 4 4 4 2 4 Butylmethoxydlbenzoyl- 2 3 2 2methane Titanium dioxide 1 5 4 2 Aerosil R972 ® 0.5 0.5 Preservative 0.50.5 0.5 0.5 0.5 0.5 0.5 Glycerol 3 5 10 10 5 10 5 MgSO₄ 1 1 NaCl 0.5 10.2 1 Phenylbenzimidazole- 2 4 sulphonic acid Sodium hydroxide solution,0.8 1.3 45% Water ad 100 ad 100 ad 100 ad 100 ad 100 ad 100 ad 100

1. Cosmetic or dermatological preparation which are finely dispersewater-in-oil system comprising
 1. an oil phase,
 2. a water phase,
 3. atleast one modified phyllosilicate which exhibits both hydrophilic andlipophilic properties and positions itself at the water/oil interfaceand
 4. said preparation is emulsifier-free.
 2. Preparation according toclaim 1, wherein the further cosmetic or pharmaceutical auxiliaries,additives and/or active ingredients are present.
 3. Preparationaccording to claim 1, wherein the content of one or more modifiedphyllosilicates is between 0.05% by weight and 10% by weight based onthe total weight of the preparation.
 4. Preparation according to claim1, wherein in addition to one or more modified phyllosilicate, furtherpigment(s) is/are present wherein said further pigment(s) is/areselected from the group consisting of modified polysaccharide(s),microfine polymer particle(s), micronized inorganic pigment(s) andmixtures thereof.
 5. The preparation of claim 4, wherein said micronizedinorganic pigment(s) is/are amphiphilic metal oxide(s).
 6. Thepreparation of claim 5, wherein said amphiphilic metal oxide(s) is/areselected from the group consisting of titanium dioxide, zinc oxide, ironoxide(s), silicon dioxide, silicate(s) and mixtures thereof. 7.Preparation according to claim 2, wherein said further cosmetic orpharmaceutical auxiliaries, additives and/or active ingredients are UVfilter substances.
 8. Preparation according to claim 7, wherein said UVfilter substances are unsymmetrically substituted s-triazine derivativesselected from the group consisting of2,4-bis{[4-(2-ethylexyloxy)-2-hydroxy]phenyl}-6-(4-methoxyphenyl)-1,3,5-triazineand diocylbutylamidotriazone.
 9. Preparation according to claim 2wherein said further cosmetic or pharmaceutical auxiliaries, additivesand/or active ingredients are sulfonated UV filters selected from thegroup consisting ofphenylene-1,4-bis(2-benzimidazyl)-3,3′-5,5′-tetrasulfonic acid and itssalts; benzene-1,4-di(2-oxo-3-bornylidenemethyl-10-sulfonic acid) andits salts; 3-phenylbenzimidazole-5-sulfonic acid and its salts; andsulfonic acid derivatives of 3-benzylidenecamphor and salts thereof. 10.Preparation according to claim 1 further comprising one ore moreadditives or active ingredients selected from the group consisting ofastringents, antimicrobially active substances and substances effectiveagainst acne.
 11. Preparation according to claim 3, wherein the contentof one or more modified phyllosilicate(s) is/are between 0.1% by weightand 2% by weight based on the total weight of the preparation.